TW200900474A - Transition metal-containing effect pigments - Google Patents

Abstract

The present invention relates to effect pigments comprising transition-metal oxides or transition-metal hydroxyoxides or transition-metal hydroxides based on flake-form substrates which are uncoated or coated with one or more metal oxides, and to the use thereof, inter alia in paints, coatings, printing inks, plas-tics and in particular in cosmetic formulations.

Description

200900474 IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to effect pigments containing transition metal oxides or transition metal hydroxides or transition metal hydroxides and in the form of uncoated or coated sheet substrates. Bottom, as well as its application, especially in lacquers, coatings, printing inks, plastics, especially in cosmetic formulations. [Prior Art] Pigments containing layers of oxides/hydroxides including transition metal compounds, for example, F e2 0 3 , are used as gloss or effect pigments in many fields of the industry, especially for decorative coatings, plastics, lacquers. , paint, printing ink and cosmetic formulations. For improved properties, the application medium typically includes a number of additives such as plasticizers, tanning agents, stabilizers, anti-aging agents, lubricants and mold release agents, antistatic agents and color formers. An unwanted interaction is often observed, in particular, the interaction between the effect pigment and the additive in the application medium, which is generally considered to be involved in the reaction of the transition metal cation with the organic additive. Therefore, it is often observed in the plastic that the stabilizer and/or the aging agent molecules diffuse onto the surface of the pigment particles to cause a yellowing reaction, and the yellowing reaction is also carried out in the dark, especially if the plastic is included as an antioxidant or heat. The phenolic component of stabilizers or UV stabilizers. A plastic having a phenolic component is yellowed even if the pigment concentration is as low as 0.01% by weight. In particular, if there are stereoscopically accessible phenolic compounds in the plastic, the yellowing reaction during processing may already be apparent. Conversely, -4- 200900474, if it is a compound that is not easily accessible in steric form, it sometimes happens to yellow after 18 months of processing. In general, in the case of processing at 80 ° C and the pigment concentration is 'e.g., 0.1% by weight, the yellowing reaction can be visually observed within 2 hours. The yellowing reaction causes unattractive effects, especially when the pigment is lighter in color, which considerably destroys the aesthetic impression of the plastic system. However, when the pigment concentration is extremely low, yellowing occurs even in the dark color. The cause of the yellowing reaction is usually caused by the photoactivity of a transition metal layer composed of, for example, TiO 2 , Fe(OH) 3 , FeOOH, Fe 203, Fe 304, CrO 3 , ZnO or a mixed oxide thereof. It accelerates the photodecomposition reaction of organic components in plastics or paints. WO 2006/0 1 8 1 96 specifically discloses a post-coated interference pigment based on a coated glass sheet having a significantly low photoactivity, for example, compared to a Ti Ο 2 coated mica pigment. This conventional technical pigment also significantly slows the degradation of dihydroxyacetone (D Η A) in the self-tanning formula for makeup. However, the conventional art pigment is a highly transparent interference pigment having a TiO02 coating based on a glass sheet, i.e., a pigment having no inherently absorbed color (mass tone). However, in cosmetics, it is also preferred to obtain an effect pigment having an attractive beige to reddish brown absorption color and having DHA stability in combination with an iron-containing effect pigment. Cosmetic formulations comprising effect pigments containing iron oxide or hydroxide layers generally have only very limited chemical stability (because of the chemical interaction of the pigment surface with the cosmetic active compound), in addition to causing decomposition of the cosmetic active substance, Significantly reduce the shelf life of the formulation. SUMMARY OF THE INVENTION -5- 200900474 Therefore, the object of the present invention is to find an effect pigment having a transition metal oxide or hydroxide layer, in particular a layer having an iron oxide or a ferric hydroxide layer, the layer being Substantially photochemically or thermochemically inactive, so it does not, or only to a low degree, form a complex with the organic matter in the formula 'and because of its attractive beige to red plucking color', it can be used as a cosmetic formula. Skin-corrector pigment. Unexpectedly, it has now been found that an effect pigment having a flaky matrix as a base and comprising an oxide/hydroxide of a transition metal can be stabilized if it has a layer of SiO 2 and/or Al 2 作为 3 as an outer layer. Encapsulation of the transition metal oxide/hydroxide layer with SiO 2 and/or Al 2 〇 3 or its hydrate SiO x (OH) y / A 100 H to completely or substantially inhibit chemically unstable organic matter and chemical reactivity in the applied medium Direct contact of the transition metal oxide/hydroxide surface. Because of the natural color of such effect pigments, it can, for example, be present only in the presence of transition metal oxides (eg, iron oxides or hydroxides) in cosmetic formulations (eg, day creams, foundations, or self-staining sunscreens). An organic substance having a very limited chemical stability 'for example, dihydroxyacetone, a cosmetically active compound such as a UV filter' or the like. The shelf life affected by the destruction of the cosmetic active material is significantly improved by the use of the pigment of the present invention. Further, in the example of coloring the effect pigment of the present invention, it was observed that the yellowing of the paint and the plastic was slow. The present invention therefore relates to the fact that an effect pigment based on an uncoated or coated flaky substrate is highlighted by the fact that the surface layer of the pigment is included as a final layer comprising the following layer package (A) An oxide of iron and/or an oxygen hydrated layer of iron, 200900474 and (B) SiO 2 and/or Al 2 〇 3 or a hydrate layer thereof, or a layer group comprising the following as a final layer: (A) a layer comprising a mixed oxide, hydroxide, oxygen hydrate or double hydroxide of the formula: M^M^OJOHhXz, wherein Μ 1 = F e > Μ 2 =M g11, Ca11 , i 3rn, Ba11, γ· III/IV -ZrIV : , Crm, Fe1 Ι/1ΙΙ , CoII/in , Ni11 , Cu11 , Ag1 , Zn11 , AlnI , Gain , Sn1 I/IV , Sbm / lv , Bim , X = =Cl·,NO Γ,S〇4 ,2- > C〇32· ' 3,w = 0- 3,χ = 0·6,y = 0- 12,z = 0_ where v + w>0 And x + y > 〇, and v, w, X and y may also be non-integer coefficients in the case of the suboxide, and (B) 5丨02 and/or Al2〇3 or a hydrate layer thereof. The effect pigment of the invention is particularly suitable for coloring plastics, since encapsulating the transition metal oxide/hydroxide layer with Si〇2 and/or Al2〇3 means that the chemical reactivity on the surface is remarkably low, so especially when there is phenol in the plastic When the components are part, the yellowing is strongly suppressed. Since the natural color of the effect pigment of the present invention is very suitable for use in a cosmetic formulation including an organic substance such as an organic active compound, a U V filter or the like. The effect pigments of the present invention dramatically increase the shelf life of formulations containing organic materials that are sensitive to transition metals. Further, the effect pigment of the present invention is very suitable for use as a so-called "skin correction agent" pigment, for example, for use in ointments' creams and compacts. "Skin Corrector" is generally different in that it can compensate for uneven color of the skin (for example, red dots, dark circles), that is, the unevenness or ideally fully compensated for the unevenness of the color of the skin region by its inherent color. The skin tone is uneven. However, if the characteristic gloss of such pigments causes the skin to appear "greasy" in some cases after application, it is not suitable for this application. If the surface of the effect pigment of the present invention is covered with an iron-containing hydroxide or a double hydroxide, the disadvantage can be circumvented. These layers act as scattering centers for the incident light, so the pigment is reduced in light without unduly weakening the interference color and is not suitable for this application. In the case of iron-containing hydroxide or double hydroxide, it is particularly advantageous because it contributes to the 'skin correction agent' pigment's extra skin tone and beige to brown absorption color. Therefore, the present invention also relates to the use of the pigment of the present invention as a skin color correcting agent and a pigment. The base substrate to which the effect pigment of the present invention is applied is preferably a transparent sheet, for example, a glass sheet, a synthetic or natural mica sheet, a Si〇x sheet (x = 2 2 〇, preferably χ = 2) ' Α 12 〇 3 sheets, Ti 〇 2 pieces, synthetic or natural iron oxide sheets, optionally passivated metal sheets, for example, aluminum sheets, aluminum bronze, brass bronze, zinc bronze, titanium bronze or other equivalent sheets, graphite sheets, liquid crystal polymer (10)) mu sheets Or a mixture of the aforementioned tablets. The preferred matrix mixture is of the following composition: - Synthetic or natural mica flakes + Al2〇3 flakes" Synthetic or natural mica flakes + glass flakes or natural iron oxide flakes VIII ^ 虱 籾 籾 籾 成 成 成Mica flakes, 'flakes or bronze + synthetic or natural mica flakes-8 - 200900474 - Aluminium flakes or bronze + Α12〇3 flakes - Mice or bronze + glass flakes - BiOCl flakes + glass flakes - BiOCl flakes + synthetic or natural mica flakes Preferably, the Si〇2 sheet used is synthetic, doped or undoped with a uniform layer thickness, preferably undoped 'SiO 2 sheet, and cured and hydrolyzed, for example, on a continuous strip of water-glass solution. And manufactured as described in WO 93/0823 7. Herein, the uniform layer thickness means that the layer thickness tolerance of the total dry layer thickness of the particles is from 3 to 10%, preferably from 3 to 5%. The flaky cerium oxide particles are usually in an amorphous form. Such synthetic sheets are superior to natural materials, such as mica, in that layer thickness can be set with desired properties and layer thickness tolerances are limited. The special glass sheets can be composed of all glass types known to those skilled in the art, for example, Ca/Al borosilicate glass, window glass, C glass, E glass, ECR glass, Duran® glass, laboratory equipment glass, optical glass. . Particularly preferred are E glass, ECR glass and Ca/Al borosilicate glass. The refractive index of the glass sheet is preferably from 1.45 to 1.80, particularly from 1.50 to 1.70. Glass-doped glass sheets are more suitable as a preferred substrate. Suitable dopants are, for example, Fe, Bi, La, Nb, Ba, Ti' V, Ce, Au and Cu or mixtures thereof. Because of doping, it is possible to utilize a glass having a special property 'e.g., a refractive index of up to 2.3 or a strong intrinsic color. Suitable substrates are preferably based on Ca/Al borosilicate (for example, Ronastar® from Merck KGaA), SiO 2 (for example, Colorstream® from Merck KGaA) 'Al2〇3 (eg ' Xirallic0 ' from Merck KGaA ), natural leaf iron oxide (for example, ΜΙΟΧ®, available from 200900474 K^rntner Montan Industrie), graphite, synthetic flake iron oxide (eg, TAROX®, available from Titan Kogyo) or metal The matrix matrix mixture may also have an appearance formed by mixing the individual pieces of different particle sizes. In this case, it is preferred to have different particle sizes, for example, 1-15 μm, 1-25 μm, 3-8 μηι, 3-10 μηι, 5-25 μηι, 5-30 μηι, 5-50 μ m, 1 7 - 2 6 μ m, 1 0 - 6 0 μ m, 5 _ 1 0 0 μ m, 1 0 - 1 0 0 μ m, 1 0-12 5 μm > 10-150 μιη, 20- 1 80 μιη , a mixture of 20-200 μηι, 45 -5 00 μm mica flakes. Specific properties and appearances are well known to those skilled in the art by suitable selection of particle size in the mixture. For example, the following: a mixture of particles having a narrow particle size distribution has a high color brightness; from fine particles (preferably 1-25 μm) and coarse particles (preferably 2100 μηι, especially 1 0 0 to 500 μm) The composition of the mixture has both high hiding power and scintillation. The size of the base matrix itself is not critical as long as it is suitable for the particular application. Usually, the thickness of the sheet-like substrate is between 0.05 and 5 μm, in particular between 〇 1 and 4.5 μηη. The glass sheet preferably has a thickness of S 1 μηι, particularly < 900 nm, and most preferably < 500 nm. The other two-dimensional size is usually between 1 and 25 0 μηη, preferably between 2 and 200 μηι, especially between 5 and 150 μm. The particle size is obtained by measuring the powder or pigment suspension via laser diffraction using a commercially available instrument known to those skilled in the art (e.g., from Malvern or Horiba). The matrix preferably has a form factor (r (aspect ratio: diameter -10-200900474 / thickness ratio) of 5 to 750, particularly 1 〇 _3 〇〇, and most preferably 20 to 200. The base substrate can be uncoated or coated with one or more 'preferably colorless, metal oxides, particularly high refractive index metal oxides, single or multiple. Metal oxides which may be mentioned are, in particular, Ti 〇 2 which is a rutile or anatase variant, an oxidation pin 'tin oxide, zinc oxide, cerium oxide. The base substrate is preferably covered by one, two, three or four layers, in particular a layer of metal-oxide. If the base substrate has three oxide layers, it is preferably alternating high and low refractive index layers, for example, a Ti〇2-Si〇2_Ti〇2 layer sequence. The best base matrix is natural and/or synthetic mica flakes, Si〇2, Al2〇3, Fe2〇3, glass “passivated aluminum”, made of aluminum bronze, brass bronze, zinc bronze, titanium bronze or A piece of material made of TiO2 coated with mica, glass, SiO 2 or A12 ,, or coated with SiO 2 -SiO 2 -Ti 〇 2 mica, glass, Si 〇 2 or Al 〇 3, via Si 〇 2 -Ti02 coated glass sheet, via Si〇2-

Ti02-Si02-Ti02 coated glass flakes, coated with Si〇2 or glass of ai2o3. Therefore, the special matrix has the following structure: Substrate+high refractive index metal oxide+layer (A)(B) Substrate+SiO2 +high refractive index metal oxide + layer group (A) (B) matrix + layer group (A) (B ;) matrix + SiO 2 + layer group (A) (B) matrix + high refractive index metal oxide + low refraction Rate metal oxide + high refractive index metal oxide + layer group (A) (B) matrix + SiO 2 + high refractive index metal oxide + low refractive index metal oxide + high refractive index metal oxide + layer group (A) (B) -11 - 200900474 The refractive index of the coated or uncoated substrate is preferably from 1.20 to 2.20, especially from 1 to 50 to 1.70. However, the refractive index of the post-coated substrate itself is not a critical parameter. Therefore, the scope is to be considered as illustrative and not limiting. In the case of a metal sheet, a substrate having a higher refractive index is naturally also suitable. In the present case, the 'high refractive index coating means a layer having a refractive index > 1.8, and the low refractive index layer means n S 1.8. If the substrate sheet is covered with a TiO 2 layer, the TiO 2 may be a rutile or anatase variant. It is preferably in the form of rutile. In this case, it is preferred to cover the full area or partial coverage of Sn02 or the partial coverage of the Sn02 core before covering with Ti〇2. The ultra-thin Sn02 layer has a thickness of at most 10 nm, preferably < 5 nm, the layer (A) is preferably an iron oxide (hydroxide) layer, a mixed oxide layer or a double hydroxide, especially Fe203, Fe3〇4, FeOOH, FeTi03, Fe2Ti05, Fe(0H)3/Ca(0H)2 mixture, Fe(OH)3/Al(OH)3 mixture 'Fe(OH)3/Zn(OH)2 mixture Or a layer of a mixture of Fe(OH)3/Mg(OH)2. The mixing ratio in the hydroxide mixture may be from 〇.1:99.9 to 99.9: 0.1 parts by weight. The thickness of layer (A) on the coated or uncoated substrate can of course vary over a wide range depending on the desired effect. The layer (A) preferably has a thickness of 2 to 35 〇 nin, particularly 5 to 200 nm. In order to control the hue, gloss and color intensity, a layer thickness of 2 〇 15 〇 nm is preferred. The low refractive index coating (B) is used for the encapsulating layer (A), and is preferably composed of Si〇2 and/or AUC»3. When it is a mixture of Si〇2 and ai2q3, the ratio of mixing -12-200900474 is 1:100 to 100:1, preferably 1:5〇 to 50:1, especially 1:10 to 10:1. The layer (B) may further comprise 0.005_1 (% by weight), preferably 0.01 to 8% by weight 'particularly 0.05 to 5% by weight, selected from the group consisting of V, Zr, Zn, Ce' Ti' B' Na' K' Mg' An oxide or hydroxide of Ca and/or Μη. Among these oxides and hydroxides, oxides and hydroxides of V, Zr, Ce and/or Zn are particularly preferred. The thickness of the final layer (B) is 2_2 〇〇 nm, preferably 10-80 nm ', especially 10-60 nm. In the particularly preferred effect pigment of the present invention, the proportion of the layer (B) is from 5 to 60% by weight, particularly from 1 0 to 30% by weight, particularly preferably from 1 2 to 20% by weight, based on the total amount of the pigment. The oil absorbing dam of the effect pigment according to the invention (measured according to DIN EN ISO 7 8 7-5: 1 995 - 10) is preferably from 5 to 100, in particular from 5 to 50, particularly preferably from 20 to 40. However, the oil absorbing sputum of the pigments of the invention is not critical per se. The iron ion-containing pigments of the present invention are not only highlighted by their attractive optical effects, but also because of the significantly improved polymer shelf life, particularly in phenol-containing plastics and coatings. Furthermore, these pigments are distinguished by increased mechanical stability. Compared with the effect pigment which has not been passivated by layer (B), the pigment of the invention only observes slight light/dark yellowing or no yellowing in the plastic, that is, the pigment of the invention has only a slight plastic component, if any Word, surface reaction. The invention further relates to the use of the effect pigments of the invention in the following: paints, coatings, in particular automotive paints, industrial coatings, powder coatings, printing inks, security printing inks, plastics, ceramic materials, glass, paper, electrophotographic Toners, seeds, greenhouse cloths and tarpaulins for printing methods, and as an absorbent in the laser markings of paper and plastic-13-200900474, used as absorbents in laser welding of plastics and Application in cosmetic formulations. The pigments of the invention are further suitable for the manufacture of pigment pastes with water, organic and/or aqueous solvents, for the manufacture of pigment compositions and for the manufacture of dry preparations, for example, granules, tablets, granules, briquettes and the like. Dry preparations are particularly suitable for use in printing inks and cosmetics. Particularly preferred effect pigments of the invention are as follows: Substrate + (Si02) + Fe203 + Si〇2 Substrate + (Si02) + Ti02 + Fe203 + Si02 Substrate + (Si02) + Ti02 + Si02 + Ti02 + Fe203 + Si02 Substrate + ( Si02) + FeOOH + Si02 matrix + (Si02) + Ti02 + FeOOH + SiO 2 matrix + (Si〇2) + Fe2Ti〇5 + Si02 matrix + (Si02) + Ti02 + Fe2Ti05 + Si02 matrix + (Si02) + FeTi03 + Si02 Substrate + (Si02) + Ti02 + FeTi03 + SiO 2 Substrate + (Si02) + Fe(OH)3/Mg(OH)2 + Si02 Substrate + (Si02) + Ti02 + Fe(OH)3/Mg(OH)2 + Si02 matrix + (Si02) + Fe(OH)3/Ca(OH)2-+ SiO 2 matrix + (Si02) + Ti02 + Fe(OH)3/Ca(OH)2+ Si02 matrix + (Si02) + Fe304 + Si02 matrix + (Si02) + Ti02 + Fe304 + Si02 matrix + (Si02) + Fe(OH)3/Al(OH)3 + Si02 matrix + (Si02) + Ti02 + Fe(OH)3/Al(OH)3 + Si02 Substrate + (Si02) + Ti02 + FeCa2(OH)6Cl + Si02 -14- 200900474 Substrate + (Si02) + Ti02 + FeCa2(0H)6N03 + Si02 Substrate + (Si02) + Ti02 + FeMg2(0H)6C03 + Si02 matrix + (Si02) + Ti02 + FeZn2(0H)6C03 + SiO2 matrix + (Si〇2) + Ti〇2 + Cr〇3 + Fe3〇4 + Si〇2 matrix + (Si02) + Fe(OH)3 /Zn(O H)2 + Si02 matrix + (Si02) + Fe(OH)3/Zn(OH)2 + Si02/Al203 matrix + (Si02) + Fe2〇3 + Si02 + Fe203 + Si02/Al203 matrix + (Si〇2) + Fe2〇3 + Si〇2 + Fe2〇3 + Si〇2 matrix + (Si02) + Fe3 04 + Si02 + Fe3 04 + Si02/Al203 matrix + (Si02) + Fe3 04 + Si02 + Fe3 04 + Si02 matrix + (Si02) + Fe203 + Si〇2/Al2〇3 matrix + (Si02) + Ti02 + Fe203 + Si02/Al203 matrix + (Si02) + Ti〇2 + Si02 + Ti〇2 + Fe2〇3 + Si02/Al2〇 3 matrix + (Si02) + FeOOH + Si02 / Al203 matrix + (Si02) + Ti02 + FeOOH + Si02 / Al203 matrix + (Si02) + Fe2Ti05 + Si02 / Al203 matrix + (Si02) + Ti02 + Fe2Ti05 + Si02 / Al203 matrix + (Si02) + FeTi03 + Si02/Al203 Substrate + (Si02) + Ti02 + FeTi03 + Si02/Al203 Substrate + (Si02) + Fe(OH)3/Mg(OH)2 + Si02/Al203 Substrate + (Si02) + Ti〇2 + Fe(OH)3/Mg(OH)2 + Si02/

Al2〇3 matrix + (Si02) + Fe(OH)3/Ca(OH)2-+ Si02/Al203 -15- 200900474 matrix + (Si02) + Ti02 + Fe(OH)3/Ca(〇H)2+ Si02/Al203 matrix + (Si〇2) + Fe3〇4 + Si〇2/Al2〇3 matrix + (Si〇2) + Ti〇2 + Fe3〇4 + Si〇2/Al2〇3 matrix + (Si〇 2) + Fe(〇H)3/Al(OH)3 + Si02/Al203 Substrate + (Si02) + Ti02 + Fe(OH)3/Al(OH)3 + Si02/Al203 If the substrate is glass or aluminum, This substrate is preferably directly covered with a layer of S i Ο 2 . In the application of the invention as a "skin correction agent" pigment, the substrate used is preferably natural or synthetic mica and/or glass flakes, in particular natural or synthetic mica or glass flakes coated with Ti〇2 (rutile). Any SiO2-coated glass flakes. The metal-oxide (hydroxide) layer is preferably applied by wet chemical methods, and may be developed by wet chemical coating methods developed for the preparation of effect pigments. Such methods are described, for example, , DE 14 67 468, DE 19 59 988, DE 20 09 566 1 DE 22 1 4 545, DE 22 15 191, DE 22 44, 298, DE 23 1 3 3 3 1, DE 1 5 22 572, DE 3 1 3 7 8 0 8, DE 3 1 3 7 8 0 9, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602 ' DE 3 2 3 5 0 1 7 or described in the technical field Other patent documents and publications are known to those skilled in the art. In the wet coating example, the matrix particles are suspended in water at a pH suitable for hydrolysis and the pH is selected such that the metal oxide or metal oxide hydrate precipitates directly on the sheet. One or more hydrolyzable metal salts or water-glass solutions are added without secondary precipitation. The pH is usually At the same time, the alkali and/or acid are metered in and kept constant. Then the pigment is separated, washed and dried at 50-150 ° C for 6 - 18 hours, and then if necessary, the calcined layer is further calcined. 5 - 3 small -16- 200900474, wherein the calcination temperature is adjusted and optimized according to the coating in each case. Usually, the calcination temperature is between 500 and 1 ° C (preferably between 600 and 900 ° C) Depending on the substrate and the coating, in the hydroxide oxide, for example, FeOOH > and the hydroxide/hydroxide mixture, for example, Fe(OH)3/Mg(OH)2 or FeCa2(OH)6N〇 In the example of 3, the calcination step is omitted and the pigment is dried only at a maximum of 120 ° C. If desired or if each layer sequence is desired (for example, the hydroxide layer is on the oxide layer), the pigment can be separated and applied. After each coating, it is dried and calcined arbitrarily, and then resuspended to precipitate other layers. The SiO 2 is chromatographed on a substrate and usually added with a water-glass potassium or sodium solution at a suitable pH. It is carried out by gas phase coating in a fluidized bed reactor, so it can be used, for example, EP 0 045 8 5 1 and EP 0 1 06 2 35. The method of preparing an effect pigment. The hue of the effect pigment of the present invention can be varied over a wide range by selecting different layer compositions, the layer combination 'coating amount or the obtained layer thickness. Fine tuning of a hue' except for the amount of simplicity In addition to the selection, the desired color can be achieved under the control of visual or measurement techniques. The absorption color of the iron-containing coating of the dry S pigment can be specifically adjusted by a number of adjustment means. It is, for example: • The precipitation of Fe(〇H)3 or FeOOH-the color of the pigment can be adjusted by the amount of precipitation of the hydroxide. • Fe(〇H)3 or FeOOH combined with white alkaline earth metals, alkali metals or transition metal hydroxides, for example, Ca(〇H)2, Mg(〇H)2, Al(〇H)3 -17- 200900474 , precipitation of Zn(OH)2. The mixing ratio determines the brightness and yellowness of the coating. Further, the color of the pigment can be adjusted by the amount of precipitation of the hydroxide mixture. - Precipitation of an iron-containing double hydroxide of the general formula [FeM22OH]6]X. Here, M2 may be =Mgn, Ca11, Sr11' Ba11, Zn11. In this case, the stoichiometric ratio of Fe3 + to Μ2 has been predetermined. Then the color of the pigment can be adjusted by the amount of precipitation of the complex hydroxide and the color of the ruthenium 2 cation. In the above three cases, the final color of the pigment may additionally be specifically affected by the drying or calcination temperature. Due to the content of iron ions or other transition metal ions, it is of course possible to adversely affect shelf life (because cosmetic actives and/or organic formula components are destroyed). Therefore, in this case, it is also advantageous to thermally and photochemically passivate these "skin correction agent" pigments with SiO 2 and/or A 12 0 3 layers. In order to improve the light, water and climate stability, depending on the application, it is generally recommended that the finished pigment product be post-coated or post-treated. Suitable post-coating or post-treatment is, for example, the method described in German Patent 2 2 1 5 1 9 1, D E - A 3 1 5 1 3 5 4 ' DE-A 32 35 017 or DE-A 33 34 598. Post-coating further enhances chemical and photochemical stability or simplifies pigment handling, especially when incorporated into a variety of media. In order to improve the wettability &/or compatibility of the medium to be used, a functional coating such as Al2?3 or ZrO2 or a mixture thereof may be applied, for example, to the surface of the pigment. Furthermore, the organic post-coating can be carried out, for example, with decane, for example, EP 〇〇9 0 2 5 9, EP 〇 634 45 9, Wo 99/57204, WO 96/3 2446, WO 99/5 7204, - 18- 200900474 US 5,75 9,25 5,Us 5,5 7 1,8 5 1,WO 0 1 /92425 or JJ Ponjee,Philips Technical Review, V o 1. 44, No. 3,81 f f. , and PH Harding JC Berg, J. Adhesion Sci. Technol. Vol. 11 No. 4, pp. 471-493 5 households. The choice of final post-coating is only limited by the fact that it should ensure that the surface-reactive transition metal compound or transition metal cation is not reintroduced into the final product in large amounts. The pigments of the present invention having a natural color are compatible with a number of color systems, preferably selected from the group consisting of paints, coatings, printing inks, and cosmetic formulations. For the preparation of printing inks, for example, gravure, flexographic, lithographic, lithographic overprint varnishes, many binders, especially water soluble types, are suitable 'eg BASF, Marabu, Pr6ll, Sericol, Hartmann , Gebr. Schmidt, sold by Sicpa 'Aarberg, Siegberg, GSB-Wahl, Follmann, Ruco or Coates Screen INKS GmbH. The printing ink can be a water based or solvent based structure. Further, the pigment is also suitable for use in laser marking of paper and plastics, as well as in agricultural applications, for example, in greenhouse fabrics, and for example, for coloring tarpaulins. In view of the increased chemical stability of the effect pigments of the present invention, it is particularly suitable for use in polymers, particularly plastics. The plastic preferably comprises from 0.01 to 10% by weight of the pigment of the invention, especially from 0.1 to 5% by weight, particularly preferably from 0.2 to 2.5% by weight. Even at a pigment concentration as low as < 0.5% by weight, the plastic including the phenol-containing additive does not exhibit significant dark yellowing. Furthermore, this effect pigment is suitable for use in coating formulations. The effect pigment of the present invention has a natural color layer of a transition metal oxide, a transition metal hydroxide 19-200900474 oxide and a transition metal hydroxide/hydroxide mixture (for example, including Fe/Ti'Fe' Cu), and thus It has a special noble metal hue such as gold, brass, bronze, copper and is usually characterized by metallic luster and high brightness. So it can be used in various application media to achieve special effects, such as 'in cosmetic formulations, for example, nail polish, Lipstick, powder, gel, lotion, lotion, soap, toothpaste, especially for self-imaging formula. The effect pigment of the present invention, in a preferred application type, can be uniformly mixed with the cosmetically active compound. Suitable active compounds are, for example, insect repellents, inorganic UV filters, for example Ti〇2, UV A/BC protective glazing agents (for example, OMC, B3 'MBC)' can also be encapsulated, resistant Aging active compounds, vitamins and their derivatives (eg, vitamins A, C, E, etc.), as well as additional cosmetically active compounds, for example, sweet mycophenolic sterols, LPO, VTA, ectoin' oil phase Emblica, allantoin, bioflavonoids and their derivatives. Self-imaging sun cream, liquid, spray, etc., including, for example, 'self-lighting agent DHA (1,3-dihydroxyacetone) or erythro ketose or a mixture of the two substances and an effect pigment having a final layer of TiO 2 or Fe 203 Among them, DHA degraded quite rapidly in the formulation over a three month period, especially when T i Ο 2 was an anatase variant. Conversely, if the pigment of the invention is used in the formulation, the effect of DHA can be completely retained. The self-tanning agent material is usually sprayed onto the skin or applied by hand or in the form of an emulsion. Compared with the conventional art, the pigments including the pigments of the present invention and the general self-lighting agent materials such as '1,3-dihydroxyacetone and erythrodose have a shelf life of self-imitation sun cream, liquid or spray. increase. -20- 200900474 Self-imitation sun cream/spray preferably comprises 0.5 _ 5 . 〇 weight % of the effect pigment of the invention is preferably 1-3% by weight, and the amount of self-lighting material is 〇.〇1 to 2〇 weight % ' is preferably from 0_05 wt% to 1 wt%, especially 丨-8 wt%. The ratio of hydrazine (% by weight) is preferably from 1:1 Torr to 10:1 in the self-tanning agent mixture. A preferred mixture of self-tanning agents is a mixture of DHA and erythrokholose. For example, use DHA with a mixing ratio of 2:1 and 3:1: red alginose. Another preferred self-tanning agent is the so-called Dha Plus, which includes, in addition to 1,3-dihydroxyacetone and magnesium stearate, sodium metabisulfite (NhSaOs 'INCI: sodium metabisulfite) to mask/eliminate / Neutralization of formaldehyde oxime Needless to say 'The effect pigment of the present invention can also be blended with the following in various applications: organic dyes, holographic pigments, LCP (liquid crystal polymer), organic pigments or inorganic pigments (for example, transparent and Opaque white, color and black pigment), flaky iron oxide, known as transparent, colored and black gloss pigments based on metal oxide coated mica, glass, Al2〇3, Fe203, SiO2, and Passivated aluminum sheets and so on. The pigment of the present invention can be blended in any proportion with commercially available pigments and tanning materials. Examples of materials which may be mentioned are natural or synthetic mica, nylon powder, pure or fuller melamine resin, talc, SiO 2 , glass, kaolin, aluminum, magnesium, calcium, zinc oxide or hydroxide, BiOCl, Barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, carbon, and physical or chemical combinations of these materials. There is no limit to the particle type of the dip. It may be, for example, a sheet, a sphere or a needle, but may also be a completely irregular shape, as desired. -21 - 200900474 A cosmetic formulation comprising the effect pigment of the present invention may be in a lipophilic, hydrophilic or hydrophobic form. In the formulation having a discontinuous aqueous and non-aqueous phase, the effect pigment of the present invention may be present in one of the two phases or distributed between the two phases. The pH of the formulation may range from 1 to 14, preferably from 2 to 1, preferably from 5 to 8. The concentration of the effect pigment of the present invention in the formulation is not limited, depending on the application - it may range from 0.001 (required rinse product, for example, shower gel) to 100% (e.g., gloss application for special applications). The pigments of the invention may of course also be combined with any type of raw materials and adjuvants in the formulation, including, in particular, oils, fats, mashes, film formers, preservatives, surfactants, antioxidants, for example, vitamin C or Vitamin E, stabilizers, taste enhancers, oxime oils, emulsifiers, solvents such as 'ethanol or ethyl acetate or butyl acetate, and adjuvants usually associated with application properties, for example thickeners and thixotropic additives For example, bentonite, hectorite 'soda sand', sour, gelatin, high molecular weight carbohydrates and / or surface-active adjuvants. The organic UV filter is usually used in a cosmetic formulation in an amount of 〇. 5 _ 1 〇 by weight ‘preferably 1 to 8 wt% ’ The amount of bismuth used in the inorganic glazing agent is 〇 · J _ 30% by weight. The compositions of the present invention may further comprise other active compounds for skin protection or skin care. In principle, all active compounds which are known to those skilled in the art can be used. Particularly preferred active compounds are pyrimidine carboxylic acids and/or aryl quinones. -22- 200900474 Cosmetics applications may specifically mention the use of ectOin and ectoin derivatives to care for aging, dry or irritated skin. For example, 'ΕΡ-Α-0 671 161 reveals that ectoin and hydroxy ukdene can be used in cosmetic compositions such as 'powder' Xiangxiang, cleaning product containing surfactants, 'lipstick' lipstick 'cosmetic' care cream With sunscreen preparations. Cosmetic formulations can be applied in the form of, for example: solution, suspension 'emulsion' p I τ emulsion 'paste' ointment, gel, cream, liquid, powder, soap 'cleaning agent containing surfactant, oil, gas Sol and spray. Other examples of application forms are shampoos and shower preparations. Any desired carrier, adjuvant and 'other active compound may be added to the composition if desired. Ointment 'paste' creams and gels may include conventional carriers, for example, animal and vegetable fat 'wax' paraffin, starch 'xanthine gum, cellulose derivatives, polyethylene glycol 'polyoxyn' bentonite' Cerium oxide, talc and zinc oxide, or a mixture of these substances. Powders and sprays may include conventional carriers such as lactose, talc, sand, aluminum hydroxide, calcium citrate and polyamide powder, or mixtures of these materials. The spray may further comprise conventional propellants such as chlorofluorocarbons, propane/butane or dimethyl ether. The solution and emulsion may include conventional carriers such as solvents, solubilizers and emulsifiers 'eg 'water' ethanol 'isopropanol, ethyl carbonate, ethyl acetate 'benzyl alcohol' benzyl benzoate, propylene glycol; !,3_butanediol, oil, especially cotton good oil, peanut oil 'malt oil, olive oil, castor oil and sesame oil' fatty acid glyceride, polyethylene glycol and fatty acid sorbitan ester, or this -23 - 200900474 Mixture of some substances. The suspension may comprise a conventional carrier, for example, a liquid diluent such as water, ethanol or propylene glycol, a suspension medium 'for example, ethoxylated isostearyl alcohol' polyoxyethylene sorbitol and polyoxyethylene Sorbitan ester, microcrystalline cellulose, aluminum hydrated aluminate, agar and tragacanth, or a mixture of these substances. The soap may comprise a conventional carrier such as a 'fatty acid alkali metal salt, a fatty acid monoester salt' fatty acid protein hydrolase, an isosulfonate, a lanolin, a fatty alcohol, a vegetable oil 'plant extract, glycerin, sugar, or these a mixture of substances. The surfactant-containing cleaning product may comprise a conventional carrier, for example, a fatty alcohol sulfate salt, a fatty alcohol ether sulfate, a thiosuccinic acid monoester, a fatty acid protein hydrolase, an isosulfonate, an imidazoline derivative. , taurate methyl ester, sarcosinates, fatty acid indoleamine sulfate, alkanoyl betaine, fatty alcohol, fatty acid glyceride, fatty acid diethanolamine, vegetable and synthetic oil 'Lignin derivatives, ethoxylated fatty acid glycerides, or mixtures of these substances. The face and body oils may include conventional carriers such as synthetic oils such as 'fatty acid esters' fatty alcohols, oxime oils, natural oils, for example, vegetable oils and oily plant extracts, paraffin oils, lanolin oils, Or a mixture of these substances. The cosmetic composition can be present in a variety of forms. So it can be, for example, a 'solution' anhydrous composition, a water-in-oil (W/0) or oil-in-water (0/W) emulsion or microemulsion, multiple emulsions, for example, water-in-oil-in-water (w/o /w) Shape-24- 200900474 Type 'gel' solid strip' ointment or aerosol. Ecco ins can also be administered in encapsulated form, e.g., encapsulated with gelatin, wax matrices or liposomes, with a collagen matrix and other conventional encapsulating materials (e.g., 'cellulose encapsulation). In particular, wax matrices, for example, as described in DE-A 43 08 282, have proven to be advantageous. It is preferably an emulsion. 0/W emulsion is especially good. Emulsions, W/0 emulsions and 0/W emulsions were obtained in a conventional manner. Further examples are based on the following oily liquids: natural or synthetic oils and 遢'lanolin fatty acid esters, in particular fatty acid triglycerides, or based on the following oil-alcoholic liquids: lower alcohols, for example, ethanol Or glycerol, for example, propylene glycol and/or polyols, for example, glycerin, and oils, waxes and fatty acid esters, for example, fatty acid triglycerides. Solid bars consist of natural or synthetic waxes with oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances. When the composition is formulated into an aerosol, conventional propellants such as alkanes, fluorocarbons and chlorofluorocarbons are usually used. Cosmetic compositions can also be used to protect hair from photochemical damage (to avoid color changes), bleaching or mechanical damage. In this case, the suitable formulation is in the form of a rinse shampoo, lotion, gel or lotion, which is applied before or after shampooing, before or after dyeing or bleaching, or before or after perm. You can also choose a liquid or gel-like composition to shape or treat the hair, choose a liquid or gel-like composition to comb or blow, or a hair polish, a hot roll composition, or a hair colorant or bleach. Agent. The composition having light protection may include an adjuvant such as a surfactant, a thickener, a polymer, a softener, a preservative, a foam stabilizer, an electrolyte, -25-200900474 organic solvent, polyoxyl Derivatives, oils, waxes, oil repellents, dyes and/or pigments (which can color the composition itself or color the hair), or other ingredients commonly used in hair care. Therefore, the present invention also relates to the application of effect pigments in formulations, such as: paints, coatings, automotive paints, powder coatings, printing inks, security printing inks, plastics, ceramic materials, glass, paper, paper coatings, for electrophotographic printing. Toners, seeds, greenhouse cloths and tarps, used as absorbents in laser markings for paper and plastic, as absorbents in plastic laser fusion, cosmetic formulations, with water, organic and/or Aqueous solvents are used to make pigment pastes, the manufacture of pigment compositions, and the manufacture of dry formulations (eg, granules). The following examples are intended to illustrate the invention in more detail, but are not intended to limit the invention. [Examples] Example I. Preparation of Pigment Example 1: Natural Mica + Ti〇2 + FeOOH + Si〇2 2〇〇g Natural Potassium Mica (part of 10-60 μιη) is formulated into deionized water to form 1 0 The concentration of 0 g/Ι. The suspension was warmed to 8 (TC. The pH was then adjusted to 1-8 with hydrochloric acid (15% HCl). Maintaining a constant pH (achieved by 32% w/w NaOH counter-titrating) will be about 30 ml. The TiOCl2 solution (400 g /1) was metered in. After the metering was completed, the mixture was stirred for another 10 minutes. The pH was set to 4.0 with NaOH. However, at a constant pH, the metering force □FeCl3 was maintained. The solution (14.25% Fe) was subjected to FeOOH chromatography -26-200900474 in a golden green color. The mixture was stirred for another 30 minutes. The pH was then adjusted to 9 · 0 with dilute sodium hydroxide solution. 100 ml during 2 hours. A water-glass sodium solution (having a 5% citric acid content) was added while maintaining p Η constant with 2 _ 5 % sulfuric acid. The mixture was then stirred for a further 3 Torr and the hydrazine was adjusted to 7.5 with sulfuric acid over a period of 3 Torr. After stirring for 30 minutes, the supernatant reaction solution was filtered and separated, and then the pigment was coated and washed until salt-free. The pigment was dried at 110 ° C and sieved according to the desired particle size. The pigment of the present invention obtained in this manner has a gold color. The original color has a light green interference color. It contains a cerium oxide coating and the layer of this coating The thickness is about 20 - 3 5 nm. Example 2 · · Synthetic mica + Fe203 + 5% Si02 / 2.5% Al2〇3 (2 : 1) 75 g synthetic mica flakes (having a particle size of 10-5 〇 μιη) Stir in l. 5 liters of deionized water to 75 ° C. Then adjust the pH of the suspension to 3.0 with 5% hydrochloric acid. 3 wt% (based on Fe3 + content) ferric chloride solution is then metered in, while dropping A 32% sodium hydroxide solution was added to maintain a constant pH. The color properties were monitored by color measurement during pigment preparation, and the precipitation process was controlled by hue (hue angle arc tangent b*/a*). As the layer thickness increases, the hue changes from bronze to orange-red, then reddish brown, then reddish purple. When the desired end point is reached, the mixture is stirred for a further 15 minutes. The resulting pigment suspension is pH adjusted with 32% NaOH. Adjusted to 9.2 hours to add water-glass sodium solution (having a 5% acid content of 5% ' diluted with water in the ratio of 1:1 -27- 200900474; 39 ml / 1 〇 0 〇 ml water), the mixture is stirred 15 minutes 'The pH was adjusted to pH 6.5 with concentrated HCI. After the mixture was stirred for 15 minutes, add 5_33 g A1C13x6 h2 〇 with 3 2 〇g solid sodium sulphate. The resulting suspension was stirred at 90 ° C for 1 hour. Then the aqueous solution was filtered off and washed until chlorine-free. The product was dried. The product was calcined at 7 〇〇I. 3 minutes. The pigment of the invention obtained in this manner contains a cerium oxide/alumina coating having a layer thickness of about 30 nm. Example 3: Natural mica + Fe2〇3 + Si〇2 (doped with κ +) 75 g of natural mica flakes (having a particle size of 10_5 μm μη) were heated to 75 ° C with stirring in 1.5 liters of deionized water. The pH of the suspension was then adjusted to 3.0 with concentrated hydrochloric acid. Then, a 5% by weight (based on Fe3+ content) ferric chloride solution was metered in, while a 32% sodium hydroxide solution was added dropwise at the same time to maintain a constant pH. During the preparation of the pigment, the color properties are monitored by color measurement, and the precipitation process is controlled by the hue (hue angle arc tangent b*/a*). As the thickness of the precipitated iron oxyhydroxide increases, the hue changes from bronze to orange-red, then to reddish brown, and then to reddish purple. When the desired end point is reached, the mixture is stirred for a further 15 minutes. The pH was adjusted to pH 9.0 with dilute potassium hydroxide solution. During the 2 hour period, 100 ml of a water-glass potassium solution (having a 5% citric acid content) was added while maintaining ρ 恒定 constant with 2.5 % sulfuric acid. The mixture was then stirred for a further 30 minutes and the pH was adjusted to 7.5 with sulfuric acid over 30 minutes. After stirring for 30 minutes, the reaction solution was filtered and separated, and then the pigment was applied and washed. The pigment was dried at 1 〇〇 -28 - 200900474 to 150 ° C and calcined at 700 ° C for 45 minutes. The pigment obtained in this manner contains a cerium oxide coating, and this coating has a layer thickness of about 20-30 nm. Example 4: Natural mica + Fe203 + SiO 2 (the amount of Si〇2 based on base pigment varies) Example 4a: Natural Mica + Fe2〇3 (Comparative) Similar to Example 3, coating mica with Fe203 to achieve the desired color endpoint For the bronze range. The mixture was stirred for a further 30 minutes and then the supernatant was filtered to separate the coated substrate and rinsed. The pigment precursor was then dried at 150 ° C and calcined at 700 ° C for 45 minutes. The resulting pigment was used as a comparative example without post-coating and was used directly in Examples 4b and 4c for post-coating. Example 4b: Example 4a Bronze Color F e 2 Ο 3 Pigment + 1 5 % S i 0 2 200 g Calcined Bronze Pigment (having a particle size of 10-60 μιη) Prepared similarly to Example 4a, resuspended in 2.4 Rin the deionized water and stir to 7 °C. The pH was adjusted to pH 9.0 with dilute sodium hydroxide solution. A 3 83 g water-glass sodium solution (having a S i Ο 2 content of 8%) was metered in over a period of 3 hours while maintaining the pH constant with 1% hydrochloric acid. The mixture was then stirred for a further 30 minutes and then the pH was adjusted to 5 with hydrochloric acid over 30 minutes. After stirring for 30 minutes, the supernatant reaction solution was filtered and separated, and then the pigment was applied and washed until salt-free. The pigment was dried at 150 ° C and calcined at 700 ° C for 45 minutes. -29- 200900474 The pigment of the present invention obtained in this manner is bronze. Example 4c: Bronze Fe203 pigment of Example 4a + 30% Si02 200 g Calcined bronze pigment (having a particle size of 10-60 μιη) prepared in a similar manner to Example 4a, resuspended in 2.4 liters of deionized water and heated to 7 0 ° C. The pH was adjusted to pH 9.0 with dilute sodium hydroxide solution. A 766 g water-glass sodium solution (having a SiO2 content of 8%) was metered in over a period of 7 hours while maintaining the pH constant with hydrochloric acid. The mixture was then stirred for a further 30 minutes and then the pH was adjusted to 5 with hydrochloric acid over 30 minutes. After stirring for 30 minutes, the supernatant reaction solution was filtered and separated, and then the pigment was applied and washed until salt-free. After drying the pigment at 150 ° C, it was calcined at 7 ° C for 45 minutes. The pigment of the present invention obtained in this manner was bronze. II. Quantitative measurement of the reactivity of the pigment to DHA in the self-tanning formula as a comparative experiment, 5% Dihydroxyacetone and 5% pigment (from Examples 4, 4a and 4b) were each poured into a 〇/W cream and poured into an aqueous solution. (Comparative: only dihydroxyacetone) -30- 200900474 Cream formulation (phase A): Ingredients INCI Weight [°/〇] Tego Care 150 Glyceryl stearate, Steareth-26, Ceteth-20, Stearyl alcohol 8.00 Lanette 0 Whale stearyl alcohol 1.50 Tegosoft Liquid ethyl hexanoate whale stearyl 5.00 Miglyol 812 N caprylic/capric triglyceride 5.00 Abil-Wax 2434 Stearoxy dimethyl oxime 1.00 Dow Coming 200 (lOOcs) dimethyl oxime 0.50 4-hydroxybenzoic acid propyl p-hydroxybenzoate 0.05 Cream Formulation (Phase B): Raw Material INCI Weight [%] Pigment of Example 4, 4a or 4b 5.00 1,2-Propanediol Propylene Glycol 3.00 Methyl 4-hydroxybenzoate Methylparaben 0.15 Deionized Water 55.80 Cream Formulation (Phase C): Raw material INCI Weight [%] Dihydroxyacetone Dihydroxyacetone 5.00 Ionic water 10.00 Preparation: Heat phase A and B to 7 5 - 80 ° C. Add phase B quickly to phase A. Homogenize. Stir and cool and add phase C at 40t. • Sample is in isolated light Store at room temperature with 4 (3 months at TC. • Enzyme DHA determination was performed immediately after preparation (starting 値) and 3 months later -31 - 200900474. • DHA formulation requirements for stability: DHA degradation up to 20% : Sample starts at 40 ° C after 3 months DHA degradation % Example 4a Pigment (0% SiO 2 ) + 5% DHA 5.0 1.6 68.0 Example 4b Pigment (15% SiO 2 ) + 5% DHA 4.9 4.3 12.2 Example 4c Pigment (30% SiO2) + 5% DHA 5.1 5.1 0 5% DHA 4.8 4.3 10.4 -32- 200900474 III. Application example: Application example 1: Nursing self-imprinting sun cream (o/w) Ingredient INCI [%1 phase A Montanov 68 (1) Whale stearyl alcohol 'Whales dextrose glucoside 4.00 Span 60 P) Sorbitol stearate 1.50 Lanette 0 (3) Whale stearyl 1.00 Cosmacol ELI (4) Lactic acid C12-13垸Ester 3.00 Cosmacol EMI (4) DI-Malic acid-C12-13 alkyl ester 1.50 Arlamol HD (2) Isohexadecane 3.00 Dow Coming 9040 Polyoxanol elastomer blend (5) Cyclomethyl oxime Dimethyl sand oxygen crosslinked polymer 1.00 RonaCare® tocopheryl acetate (6) Tocopheryl acetate 0.50 4-propyl benzoate (6) Propyl paraben 0.05 phase B RonaCare® ectoin (6) Ectoin 0.50 Example 4b Pigment 2.00 Glycerin, Anhydrous (6) Glycerin 2.00 FD&C YellowNo. 6 W082 (8) CI 15985 0.01 Methyl 4-hydroxybenzoate (6) Methylparaben 0.15 Deionized Water Water 64.09 Phase C Sepigel 305 (1) Laureth-7, Polyacrylamide, C13-14 Isotherm 0.50 Phase D Dihydroxyacetone (6) Dihydroxyacetone 5.00 Deionized Water 10.00 Phase E Babylon Fragrance (9 Spice 0.20 Preparation = Phases A and B were separately warmed to 75t. Then let phase B and phase A mix slowly by stirring. Phase C was homogenized with phase A/B by mixing -33-200900474 with a hand mixer at 60 °C. After cooling to 40 ° C, the phases D and E were added with stirring. Note: pH23°c = 4.0 Viscosity: 1,8,600 cps (Brookfield model RVT DV-II, Helipath mandrel C, 10 rpm) at 23°C Source: (1) Seppic (2) Uniqema

(3) Cognis GmbH (4) Condea Chimica DACSp_A. (5) Dow Corning (6) Merck KGaA/Rona® (7) DD Williamson (8) L es Colorants W ackherr SA (9) D rom -34- 200900474 Application Example 2: Self-imitation 霜! Cream (o/w) Ingredient INCI 『%1 Phase A Tego Care 150 (1) Hard glyceride, Steareth-26, Ceteth-20, Stearyl 8.00 Paraffin Liquid P) Parffinum Liquidum 12.00 pourable sarcophagus (2) paraffin 2.00 Miglyol 812N (3) octanoic acid / triglyceride citrate 3.00 isopropyl myristate (4) isopropyl myristate 2.00 4-hydroxybenzoic acid Ester P) Propyl paraben 0.15 phase B 1,2-propanediol (2) Propylene glycol 4.00 Sorbitol F liquid (2) Sorbitol 2.00 Deionized water 47.40 4-Methyl benzoic acid (2) Hydroxyl Methyl benzoate 0.15 Example 1 Pigment 2.00 Phase c Dihydroxyacetone (2) Dihydroxyacetone 5.00 Deionized water 11.80 Phase D Fragrance (suitable amount) Perfume 0.50 Preparation = Warm phase A to 8 (TC, phase B warmed to 751. Slowly add phase A to phase B. Stir the mixture at 65 °C with a hand mixer 1 Zhong After cooling to 40 ° C was added with stirring and then cooled to 35t C. was added with stirring D. Note: pH23 ° c = 4.6

Viscosity: 42,5 00 mPas (Brookfield RVT, mandrel C, 10 r p m) at 2 3 °C -35- 200900474 Source:

(1) Degussa-Goldschmidt AG (2) Merck KGaA/Rona®

(3) S aso 1 Germany GmbH (4)Cognis GmbH -36- 200900474 (AV/Ο)螂 consistent} dish: Η-ε匡阳一f 8.00 5.50 5.50 ο 0.50 0.50 0.05 0.30 3.00 0.15 ,48.90 5.00 I 2.50 5.00 2.50 I 10.00 1 0.10 m 8.00 1.50 5.50 5.50 ο 0.50 , 0.50 0.05 0.30 3.00 0.15 , 57.90 I 2.00 I 〇 | 2.00 i 1.00 〇〇. 0.10 (N 8.00 5.50 5.50 1 l.oo I 0.50 0.50 1 1 0.05 1 0.30 3.00 : 0.15 丨60.90 〇I 0.50 I 11.00 0.50 I 10.00 0.10 8.00 1 5.50 I 5.50 I l.oo 1 0.50 1 0.50 I 1 0.05 1 0.30 I 3.00 1 1 0.15 1 51.40 I 5.00 5.00 I — 2.50” 10.00 0.10 Ο 8.00 I 6.50 I 1 6.50 1 0.50 1 1 0.05 ! 0.30 ! 3.00 0.15 57.20 1 2.00 1 2.00 | 〇10.00 1____ 0.10 σ\ 8.00 1.50 I 5.50 I 5.50 1.00 1 0.50 1 0.50 0.05 I 0.30 II 3.00 1 0.15 — 1 61.40 1.00 〇J 0.50 | 10.00 0.10 00 8.00 I 5.50 1 5.50 1 1 ι.οο 0.50 0.50 1 0.05 1 | 0.30 I 1 3.00 1 Lm5... | 51.40 | 1 5.00 | [2.50 1 5.00 | 10.00 | 〇.1〇 | 8.008.00 1.50 ^ | 5.50 | 1 5.50 1 l.oo 1 1 0.50 1 0.50 1 0.05 1 0.30 \ 1 3.00 1 1 0.15 1 | 58.90 | [2.00 | 〇1 2.00 | 10.00 1_ 0.10| 8.00 1 i.50 1 1 5.50 | 1 5.50 1 L_loo" 1 0.50 1 0.50 0.05 | 0.30 | 1 3.00 1 1 0.15 1 | 61.40 | 〇0.50 | ι.οο | lo.oo 1 0.10 8.00 ° 5.50 1 5.50 1 Ο 1 0.50 1 0.50 1 0.05 [0.30 | [3.00 1 1 0.15 1 | 53.90 | 1 5.00 I 1 5.00 | 10.00 〇.1〇1 Tf 8.00 1 5.50 1 5.50 1 ι.οο 1 1 0.50 1 0.50 1 0.05 1 0.30 1 3.00 1 015 Ί | 59.90 1 2.00 1 2.00 | 10.00 0.10 | ΓΟ 8.00 ° | 6.50 ] 6.50 1 0.50 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Stearyl octanoic acid/capric triglyceride 1 stearyl methoxy oxime 1 dimethyl oxime i acetic acid tocopheryl ester propyl paraben i octoin (Ectoin) propylene glycol p-hydroxybenzoic acid Methyl ester r + hydroxyacetone; Troxerutin erythrocyanide flavor component phase A Tego Care 150 Lanette O Tegosoft liquid Miglyol 812 N 1 Abil-Wax2434 Dow Corning 200 (100cs) RonaCare® Tocopherolate 4-Hydroxybenzoate Phase B RonaCare® ectoin 1,2-Propanediol 4-Hydroxybenzoate Methyl Deionized Water Phase c | Dihydroxyacetone III Hydroxyethyl-rutin Glycoside Example 2 Pigment Red alginone deionized water phase D Sunshine fragrance. A Φ αΓΤΠψ Y 啪鹧 啪鹧 鹦. Φο 恶Y Jun Dun «邈 3. 0 inch _ 辕 change. An 矸 矸 啪鹧 purple. Φ νππψ Φ Φί H 3 wants to be plastic and invites Li. Ρ08刚ΙίΙΙΗΠΙΙ4 candied fruit 0 8 _癍1IV wants honey: hit m -37- 200900474 O/AV)M1S dish: 9SI 匡旺(四) \〇(Ν ° ! 1.30 1 13.00 1 1 2.00 1 5.00 5.00 I 1 0.30 I 5.00 1 1 5.00 | 1 2.50 I 0.30 I 1 17.00 1 I 3.00 I 2.00 II 8.00 I 〇 25.60 yn (N 1.50 ° 13.00 1 2.00 1 5.00 5.00 0.30 2.00 1 2.00 | 1.00 1 0.30 II 17.00 1 3.(8) 1 2.00 1 8.00 〇34.60 Art 1 13.00 1 1 2.00 1 5.00 5.00 0.30 1.00 〇0.50 1 0.30 I 1 17.00 1 I 3.00 I 1 2.00 1 | 8.00 | 〇37.60 m (N 1 13.00 1 1 2.00 1 5.00 5.00 0.30 5.00 1 5.00 | 2.50 0.30 I 1 17.00 1 3.00 1 2.00 1 1 8.00 | 1.00 28.10 (N CN 1.50 L____ 1 13.00 1 1 2.00 1 5.00 | 5.00 | 0.30 2.00 1 2.00 | 1.00 | 0.30 I 1 18.00 1 | 3.00 1 2.00 1 1 8.00 | 1.00 34.60 Port 1.50 〇ΓΟ 1 13.00 1 1 2.00 1 5.00 1 5.00 | 0.30 1.00 1 2.00 〇0.50 0.30 1 18.00 1 1 3.00 1 2.00 1 1 8.00 | 〇1 37.10 | ° 〇rn 1 13.00 1 1 2.00 1 5.00 1 5.00 I 0.30 5.00 1 2.50 | 1 5.00 | 1 0.30 | 1 18.00 ] 1 3.00 | 2.00 1 8.00 | 〇 | 27.10 | 〇\ "13.00] 1 2.00 1 5.00 1 5.00 | 1 0.30 I 1 2.00 1 〇1 2.00 | 1 0.30 | 1 18.00 1 1 3.00 I 2.00 1 8.00 | 〇 | 34.60 | 00 ° 〇cn 13.00 [2.00 ] 5.00 1 5.00 | 1 0.30 I 1 l.oo 1 1 0.50 | 〇1 0.30 | 1 18.00 ] 1 3.00 I 1 2.00 1 1 8.00 | 〇 | 37.10 | Γ- 〇m 13.00 1 2.00 ] 5.00 1 5.00 I 1 0.30 I 1 5.00 1 1 5.00 | 1 0.30 | 1 18.00 1 1 3.00 I 2.00 1 8.00 | 〇1 29.60 | Ό Ο rn 13.00 I 2.00 | 5.00 1 5.00 I 1 0.30 I 1 2.00 1 1 2.00 | 1 0.30 | 1 18.00 1 1 3.00 I 1 2.00 1 1 8.00 | 〇| 35.60 J xr-i Ο rn 13.00 1 [2.00 1 5.00 1 5.00 ] 1 0.30 I ο 〇1 0.30 ] 1 18.00 1 1 3.00 I 1 2.00 1 1 8.00 | 〇37.60 INCI Double-PEG/ PPG-14/14, dimethyloxoxime, cyclopentaoxane, cetyl PEG/PPG-10/1 dimethyloxycarbonylcyclomethyloxy palmitate ethylhexyl oxime W 1 1 酹 slightly diethylhexyl carbonate perfume I dihydroxyacetone j Troxerutin . Ectoin & 11 E glycerol l magnesium sulfate a S? am 氍擀勧 氍擀勧 豳 ShO bO Muir E l· Alkali ingredient phase A Abil EM 97 Abil EM 90 Dow Corning 345 Ceraphyl 368 SFE 839 Tegosoft DEC 1 Babylon fragrance material | CQ ΕΠΊ 1 _hydroxylone I trihydroxyethyl rutin glycoside Example 3 pigment | Sugar I RonaCare® ectoin S 1 1 E 1 (N l glycerol, anhydrous l magnesium sulfate pentahydrate ethanol 96% Phenonip deionized water.一|汆3^-11? 鹚濶 φ(Νφί«®^.-frV wants Mniltii to invite S to 銮骓<π噢砟旺.Φ}chain锴·s 3 to Y layer.旮«§« To the end of the Li Qi grandfather: 5銮-00 -38- 200900474 13⁄4 .-^'§00

00 m 5.00 2.50 5.00 2.50 0.30 2.50 2.50 0.20 18.00 60.00 P; 2.00 1.00 2.00 ο 0.30 2.50 2.50 0.20 27.00 60.00 1.50 mo ! 0.50 1 ο 0.50 | 0.30 I ;2.50 2.50 1 0.20 1 ! 30.00 | 60.00 mm 5.00 1 5.00 1 2.50 1 0.30 I 1 2.50 1 2.50 1 0.20 I 20.50 I 60.00 J 2.00 | 2.00 1.00 I 0.30 I 2.50 —2.50 1 0.20 1 ! 28.00 ! 60.00 1.50 mmo ο 0.50 1 0.30 I 1 2.50 1 2.50 0,20 1 30.50 I [ 60.00 I CN m 1 5.00 | LA50" 1 5.00 1 0.30" 2.50 J 1 2.50 1 1 0.20 j | 20.50 | 60.00 1.50 1 2.00 | ιοο 1 1 2.00 j [0.30 | 1 2.50 1 1 2.50 1 1 0.20 1 1 28.00 | | 60.00 | | 1.50 | o 1 0.50 1 ο 1 0.30 1 1 2.50 1 Γ^·5〇Π \〇.2〇\ | 30.50 | 60.00 os (N f 5.00 | 1 5.00 ] 0.30 ί 2·5Μ 1 2-5 °Ί \ 0.20 ] | 23.00 Γ 60.00 00 (N 2.00) 2.00 1 1 0.30 | [2.50^ 1 2.50 ^ | 0.20 ] | 29.00 | 60.00 o 1.00 1 0.30 1 [2.50 1 1 2.50 1 0.20 | 31.00 | 60.00 INCI II Hydroxyacetone 1 Troxerutin | Red Alcohol Ketone | Ectoin Propylene Glycol Phenol methyl l-hydroxybenzoate l * hydroxyethyl cellulose component phase A dihydroxyacetone 1 trishydroxyethyl rutin glycoside example 4b pigment erythrozanose | RonaCare® ectoin I, 2-propanediol sorbitol F liquid 1 Methyl 4-hydroxybenzoate deionized water phase B Deionized water Natrosol 250 HHR oA3>^-fre^KaIOSOJlBz^: hit m -39- 200900474

—I 10.00 5.00 5.00 0.50 4.50 4.00 3.00 2.00 0.50 0.10 0.30 0.80 71.80 8.00 3.00 3.00 0.50 4.50 4.00 I 3.00 I 2.00 I 0.50 I 0.10 0.30 0.80 71.80 10.00 3.00 5.00 5.00 0.50 4.50 1 4.00 1 I 3.00 I 2.00 0.50 i 0.10 I 0.30 I 1 0.80 1 70.80 8.00 2.00 I 3.00 I 1 3.00 I 1 0.50 1 4.50 1 1 4.00 1 I 3.00 I 2.00 1 0.50 o.io I 0.30 0.80 66.80 | lo.oo 3.00 1 5.00 I 0.50 1 1 4.50 1 1 4.00 1 1 3.00 I | 2.00 | 0.50 1 I 0.10 0.30 I 1 : 0.80 71.00 - 8.00 1 2·00 1 3.00” 0.50 1 4.50 1 1 4.00 1 3.00 2.00 | 0.50 | 0.10 | 0.30 | 0.80 1 69.80 1 Ο 10.00 5.00 | 0.50 | 4.50 4.00 1 | 3.00 1 | 2.00 | 0.50 1 0.10 | 0.30 | 0.80 ! 69.80 1 Os m 8.00 | 3.00 1 I 0.50 | 1 4.50 1 1 4.00 1 [3.00 | | 2.00 | | 0.50 | rH o.io 1 0.30 | 0.80 1 73.00 1 INCI Dihydroxyacetone Troxerutin Ectoin Ectoin Glycerol Glycerol Diethylene Glycol Dimethyl Isosorbide Polysorbate 80 Ethylene Caramel Spice K1轲氍氍题毅轲氍氍毅! 擀缍 withdrawal E forgive Phase A Dihydroxyacetone Trishydroxyethyl Rutin Glycoside Example 1 Pigment Red Alginone RonaCare® ectoin 1,2-Propanediol Glycerin, Anhydrous Transcutol CG Arlasolve DMI Tween 80 Walnut Extract Caramel 050 Sunshine Fragrance Phenonip Deionized Water.· 0 0 -40- 200900474 ii 10.00 5.00 I 5.00 0.50 6.00 5.00 I 4.00 II 2.00 1 I 1.60 1 I 0.30 I Appropriate amount [60.60 | m 8.00 3.00 3.00 0.50 6.00 5.00 I 4.00 I 2.00 1 1.60 1 I 0.30 I Appropriate _ 66.60 (N 1 10.00 I 13.00 5.00 5.00 0.50 6.00 5.00 l 4.00 2.00 1 1.60 1 I 0.30 I Appropriate amount | 57.60 j 8.00 丨 2.00 | 3.00 I 3.00 0.50 16.00 1 I 5.00 J [4.00 [2.00" I 1.60 J j 0.30 I _ Feeding amount 1 64.60 J 1 lo.oo 1 3.00 | 15.00 0.50 1 6.00 1 15.00 4.00 | 1 2.00 j 1.60 1 0.30 Appropriate amount [62.60 | 18.00 I 1 2.00 j | 3.00 | [0.50 6.00 15^001 | 4.00 | 1 2.00 j | 1.60 | [0.30 Appropriate amount | 67.60 | 10.00 I 5.00 0.50 J 6.00 5.00 4.00 2.00 1.60 | ,0.30 _ 溷_ m 65.60 1 8.00] 3.00 0.50 j 6.00 j 5.00 4.00 1 2.00] 1.60 , 0.30 I Appropriate amount Amount of 69.60 !iNCI_^_ Dihydroxyacetone Troxerutin Citronone 1 Sugar Ectoin View 11 IE Ethoxydiethylene Glycerol Dimethyl Isosorbide Polysorbate 80 Aloe Barbadensis^ Colorant Preservative Ingredient Phase A Dihydroxyacetone Trishydroxyethyl Rutin Glycoside Example 1 Pigment Red Alginone RonaCare® ectoin 氍11 K: (NH Transcutol CG Glycerin, Anhydro Arlasolve DMI Tween 80 Aloe CON UP 10 COS. Colorant Preservative deionized water -41 -

Claims (1)

200900474 X. Patent Application 1. An effect pigment based on a sheet-like substrate or a sheet-like matrix coated with one or more metal oxides, characterized by comprising a layer package comprising the following as a final layer: An oxide of iron and/or an oxohydrate layer of iron, and (B) a layer of SiO 2 and/or Al 2 〇 3 or a hydrate thereof, or a layer group comprising the following: (A) a mixture comprising the following formula a layer of an oxide, hydroxide, oxygen hydrate or complex (d 〇ub 1 e) hydroxide, M'M^OxCOHhXz, where Μ 1 = F e, Μ 2 = Mg11 , Ca11 , Sr11 , Ba11 , TiIII/ IV, ZrIV, Crin, Fe"/n丨' c〇nnn 'Ni",Cuii,Agi,znn,Al1丨丨,Ga丨丨丨, Sn,,/lv, Sbni/iv, Biin, X = Cl. ' N〇3- ' S〇42.,c〇32·, V-1 - 3'w = 〇- 3,x = 〇- 6,y = 〇- i2,z = 0- where v + w>0 And x + y > 〇, and y in the case of the suboxide, may also be a non-integer coefficient and (B) SiO 2 and/or A 1203 or a hydrate layer thereof. 2 · If applying for patent effect cocoon 1 effect pigment, which is coated or n-coated substrate: ® from glass, synthetic or natural mica, si〇x (χ 2'〇), Ah〇 3" Ti〇a sheet, synthetic or natural iron oxide sheet, -42- 200900474 Any passivated sheet metal 'aluminum bronze, brass bronze, zinc bronze, titanium bronze sheet 'graphite sheet' liquid crystal polymer (LCP), hologram Pigments, BiOCl flakes, or a mixture of these flakes. 3 The effect pigment of claim 1, wherein the substrate is covered with -, two, three or four metal oxide layers and covered by a layer group. 4. The effect pigment according to any one of claims 1 to 3, wherein the substrate is a metal selected from the group consisting of TiO2, chromia oxide, tin oxide, zinc oxide 'cerium oxide, which is a rutile or anatase variant. Oxide coverage. 5. The effect pigment according to any one of claims 1 to 3, wherein the layer (A) is composed of Fe2〇3, Fe304, FeOOH, FeTi03, Fe2Ti〇5, Fe(OH)3/Al(OH)3 The mixture consists of a Fe(〇H)3/Ca(OH)2 mixture, a Fe(OH)3/Mg(OH)2 mixture or a Fe(OH)3/Zn(OH)2 mixture. The effect pigment of any one of claims 1 to 3, wherein the layer (A) has a thickness of 2-3 50 nm. The effect pigment according to any one of claims 1 to 3, wherein the layer (B) is composed of SiO 2 . The effect pigment according to any one of claims 1 to 3, wherein the layer (B) is a mixture of SiO 2 and Al 2 〇 3 . The effect pigment according to any one of claims 1 to 3, wherein the layer (B) is edged from v' Zr, Zn, Ce, Ti, B, Na, K, jyjg, Ca and/or Mn Oxide or hydroxide doping. 1 〇 . The effect of any one of claims 1 to 3, wherein the layer (B) has a thickness of 2-20 nm. The effect pigment of any one of claims 1 to 3 has the following layer sequence: matrix + (Si〇2) + Fe203 + Si〇2 matrix + (Si02) + Ti02 + Fe203 + Si02 matrix + (Si〇2) + Ti〇2 + Si02 + Ti02 + Fe203 + Si02 matrix + (Si02) + FeOOH + Si02 matrix + (Si02) + Ti02 + FeOOH + Si02 matrix + (Si02) + Fe2Ti05 + Si02 Matrix + (Si02) + Ti02 + Fe2Ti05 + Si02 Matrix + (Si〇2) + FeTi03 + Si02 Matrix + (Si02) + Ti02 + FeTi〇3 + Si02 Matrix + (Si02) + Fe(OH)3/Mg (OH)2 + Si02 matrix + (Si02) + Ti02 + Fe(OH)3/Mg(OH)2 + SiO2 matrix + (Si02) + Fe(OH)3/Ca(OH)2-+ SiO 2 matrix + ( Si02) + Ti02 + Fe(OH)3/Ca(OH)2+ Si02 matrix + (Si02) + Fe3 04 + Si02 matrix + (Si02) + Ti02 + Fe3 04 + Si02 matrix + (Si02) + Fe(OH) 3/Al(OH)3 + Si02 matrix + (Si02) + Ti02 + Fe(OH)3/Al(OH)3 + Si02 matrix + (Si02) + Ti02 + FeCa2(OH)6Cl + Si02 matrix + (Si02) + Ti02 + FeCa2(0H)6N03 + Si02 Substrate + (Si02) + Ti02 + FeMg2(0H)6C03 + Si02 Substrate + (Si02) + Ti02 + FeZn2(0H)6C03 + Si02 Substrate + (Si02) + Ti02 + Cr03 + Fe3 04 + Si02 -44- 200900474 Substrate + (Si02) + Fe(OH)3/Zn(OH)2 + Si02 Substrate + (Si02) + Fe(OH)3/Zn (OH)2 + Si02/Al203 Substrate + (Si02) + Fe203 + Si02 + Fe20 3 + Si02/Al203 Substrate + (Si02) + Fe203 + Si02 + Fe203 + Si02 Substrate + (Si02) + Fe3 04 + Si02 + Fe304 + Si02/Al203 matrix + (Si02) + Fe3 04 + Si02 + Fe3 04 + Si02 matrix + (Si02) + Fe203 + Si02/Al203 matrix + (Si02) + Ti02 + Fe203 + Si02 / Al203 matrix + (Si02) + Ti〇 2 + Si02 + Ti02 + Fe2〇3 + Si02/Al2〇3 Substrate + (Si02) + FeOOH + Si02/Al203 Substrate + (Si02) + Ti02 + FeOOH + Si02/Al203 Substrate + (Si02) + Fe2Ti〇5 + Si02 /Al203 Substrate + (Si02) + Ti02 + Fe2Ti05 + Si02/Al203 Substrate + (Si02) + FeTi03 + Si02/Al203 Substrate + (Si02) + Ti02 + FeTi03 + Si02/Al203 Substrate + (Si02) + Fe(OH)3 /Mg(OH)2 + Si02/Al203 Substrate + (Si02) + Ti〇2 + Fe(OH)3/Mg(OH)2 + Si02/ A1203 Substrate + (Si02) + Fe(OH)3/Ca(OH ) 2-+ Si02/Al203 Substrate + (Si02) + Ti02 + Fe(OH)3/Ca(OH)2+ Si02/Al203 Substrate + (Si02) + Fe3 04 + Si02/Al203 Substrate + (Si02) + Ti02 + Fe304 + Si02/Al203 Substrate + (Si02) + Fe(OH)3/AI(OH)3 + Si02/Al203 -45- 200900474 Substrate + (Si〇2) + Ti〇2 + Fe(OH)3/Al(OH)3 ho 12. The manufacture of a film according to the first aspect of the patent application is characterized in that the coating of the sheet-like substrate is carried out by a chemochemical method, CVD U. 1 3 . — The effect of the application of patent scope 1 is used in paints, paints, automotive paints, powder coatings, printing inks, plastics, ceramic materials, glass, paper, paper coatings, electro-optical coloring. Agents, seeds, greenhouse cloths and tarps, in the laser markings as absorbent, in plastic laser welding agent 'cosmetics formula, with water, organic and / or aqueous solvent paste, to make pigment composition and dry preparation. 1 4 . For the effect pigments of the patent application category No. 13 in the day cream, foundation, self-imaging sun cream, self-imaging spray, self-imitation 1 5 · If the effect of patent application range 13 or 14 Among them, 1,3-dihydroxyacetone and/or erythrodose are used. 1 6 . The effect of the application of the patent range No. 13 or 14 as a "skin correction agent" in cosmetic formulations. The method of h Si〇2/Al2〇3 material, the use of i or PVD method, and the preservation of printing photo-image printing in paper and plastic as absorption for the purpose of making pigments, used in the liquid. Use of pigment materials, -46 - 200900474 VII. Designation of representative drawings: (1) The representative representative of the case is: (2), the symbol of the representative figure of this representative figure is simple: no eight, if there is a chemical formula in this case , please reveal the chemical formula that best shows the characteristics of the invention: none